Composition for the control of oils floating on water

ABSTRACT

A composition of matter suitable for the confinement of oil floating on water consisting essentially of a drying oil, a carrier selected from the class consisting of liquid alcohols, ketones and ethers, and a water insoluble metallic soap catalyst. The composition is used to control oil slicks on water by dispersing said composition on the surface of the slick in an amount sufficient to confine the oil slick and thereby allow removal thereof.

llniteel tates Patent [1 1 Gilchrist et a1.

[ 5] Aug. 28, 1973 COMlOSlTlON FOR THE CONTROL OF OILS FLOATING ON WATER[75] lnventors: Ralph E. Gilchrist; Jack C. Cox, both of Houston, Tex.

[73] Assignee: Tenneco Oil Company, Houston,

Tex.

[22 Filed: Sept. 24, 1971 [21] Appl. No.: 183,620

[52] U.S. C1 252/316, 106/252, 106/253, 106/264, 210/42, 210/D1G. 21

[51] Int. Cl B0lj 13/00 [58] Field of Search .1 252/316; 210/D1G. 21;106/252, 253, 264, 310

[56] References Cited UNlTED STATES PATENTS 3,272,758 /1966 De Lew eta1. 252/354 1,916,805 7/1933 Meidert et al. 106/310 1,971,636 8/1934Baldwin 106/252 X 2,692,208 10/1954 Fisher 106/252 2,717,214 9/1955Marotta et al.... 106/253 X 2,807,553 9/1957 Fischer 106/310 X 3,198,7318/1965 De Lew 210/42 Primary Examiner-Richard D. Levering AttorneyEugene S. Coddou and Carlos A. Torres [57] ABSTRACT 4 Claims, NoDrawings COMPOSITION FOR THE CONTROL OF OILS FLOATING ON WATERBACKGROUND OF THE INVENTION The present invention relates to thetreatment of oil slicks and spills on the surface of bodies of water andmore particularly to compositions of matter suitable for confining suchoil slicks and to a method for removing such slicks and spills fromoceans, harbors, bays, lakes, rivers or the like.

As events of recent years have shown, contamination of bodies of eatersuch as harbors, bays and indeed even open water such as oceans and seascan cause disasterous results both ecologically and aesthetically. Notonly are such oil slicks harmful to marine and wild life but they maysometimes wash ashore causing untold damage in resort facilities such asbeaches. These oil slicks and spills occur from many sources such aswhen oil is being transferred from tankers to ships for refueling, whenit is being discharged from tankers into refinery storage tanks onshore, from blow-outs on offshore drilling rigs, from sinking ordamaging of tankers, from breaks in underwater pipelines, etc.

Several methods of controlling or treating oil spills and slicks havebeen proposed. For example, various mechanical and quasi-mechanicaldevices such as fences, booms, skimmers and the like have been employedin an attempt to physically contain and/or remove the oil from thewaters surface. In several cases, straw has been strewn over the surfaceof the oil slick to absorb the oil after which the straw is collected byscooping, racking or some such method or removing it from the surface ofthe water. While these mechanical devices are relatively effective incalm waters, they are virtually useless in open waters where wave actionseverely curtails their operation. It has also been proposed to usecertain chemical means for treating slicks and spills. Most chemicaltreatments proposed have involved emulsification of the oil withresultant dispersion in the body of water or some treatment whereby theoil is caused to sink to the ocean floor. Neither of these techniques isdesirable from an ecological point of viewed inasmuch as the oil isactually not removed from the body of water but is simply removed fromthe surface thereof. Moreover, the chemical formulations used toeffectuate such treatments are generally harmful per se to marine lifethus making their use undesirable.

US. Pat. Nos. 3,198,731 and 3,272,758 teach methods and compositions oftreating oil slicks wherein a substance is dispersed over the surface ofthe oil slick which causes the slick to congeal to a substantially stiffmass or gel thus making the slick ameanable to mechanical removal.Specifically, US. Pat. No. 3,272,758 teaches the use of a compositioncomprising soaps of fatty acids derived from wool grease dissolved in asuitable hydrocarbon diluent to cause gel formation of the oil. Thefatty acids derived from wool grease and used in the aforementionedcompositions are relatively expensive and accordingly the use of thesoaps thereof is uneconomical when employed on a large scale which isgenerally the case in large oil spills such as occur if a tanker sinksor an offshore well blows out. Moreover, the soaps must first beprepared from the wool grease fatty acids which again increases thecost.

SUMMARY OF THE INVENTION It is therefore an object of the presentinvention to provide a relatively inexpensive composition of mattersuitable for controlling oil slicks and spills on water.

Another object of the present invention is to provide a composition ofmatter capable of confining an oil slick or spill on the surface of abody of water.

Still another object of the invention is to provide a composition usefulin the removal of oil slicks and spills from bodies of water whichcomposition is virtually harmless to marine life.

An important object of the present invention is to provide a method forremoving oil slicks and spills from the surfaces of bodies of water.

These and other objects of the present invention will become apparentfrom the description given herein and the appended claims.

In accordance with the above stated objects, the present invention, inone embodiment, provides a composition of matter suitable for confiningoil floating on the surface of water comprising a drying oil and a car'-rier for the drying oil. The carrier is of a type which is substantiallynon-toxic to marine life in the amounts employed.

In another embodiment, the above objects are accomplished by a method oftreating an oil slick or spill on the surface of a body of water so asto render the slick ameanable to mechanical or other such removal whichcomprises dispersing on the slick or spill the aforementionedcomposition in an amount sufficient to effect a confing of the oilslick.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel compositions of thepresent invention, as noted above, are comprised of a drying oil and acarrier which in most instances will be a solvent for the particulardrying oil employed. The term drying oil as used applies to a substancewhich, when applied as a relatively thin film, exposed to air, possessesthe property of forming a relatively tough, elastic material or film.These drying oils are, in general, liquids and derived from naturallyoccuring products but may be synthetically produced. The drying oilscontemplated by the compositions of the present invention containunsaturated fatty acids, glycerol esters of unsaturated fatty acidsand/or mixtures thereof. It is postulated that the drying ability ofsuch oils whereby they will form a durable, dry and sometimes even hardfilm when exposed to air is a result of addition polymerization inducedby reaction with oxygen; however, the precise mechanism of chemicaloxidation or polymerization responsible for the hardening process of thedrying oils is very complex and poorly understood.

As noted, the drying oils generally will be those derived from naturallyoccuring products. Non-limiting examples of naturally occurring productsinclude linseed oil, tung oil, perella oil, soybean oil, fish oil,castor oil, tall oil, olive oil, cottonseed oil, peanut oil, Chinesewood oil, etc. All of the above mentioned products plus numerous othersare known to contain one of the following components: unsaturated fattyacids, glycerides of unsaturated fatty acids or mixtures of the lattertwo. Compositions in which tall oil is employed have been found to beparticularly useful primarily because of their relatively low cost. ingeneral, any naturally occuring product containing at least one of theabove specified components in an amount sufficient to bring it withinthe definition of drying oil as that term is used above can be employedin the composition of the present invention. While, as noted, the dryingoils will primarily be derived from naturally occurring products, it iswithin the scope of the invention to use synthetic materials, i.e.,materials containing one of the above enumerated components such asunsaturated fatty acids, their glycerides or mixtures thereof, whichhave been prepared by mixing the pure components in the desiredproportion or by using the pure components themselves. Because ofeconomy, however, it is preferred that the naturally occurring productsbe employed.

The amount of the drying oil employed in the composition of the presentinvention will depend to some extent upon the amount of unsaturatedfatty acid, their glycerides or the mixture thereof present in theparticular drying oil. If the drying oil is prepared synthetically, thiscan be carfully controlled. When the drying oil comprises a naturallyoccurring product such as those enumerated above, the amount of thenaturally occurring product used in the compositions will be dependenton the amount of the particular unsaturated fatty acids, fatty acidglycerides and/or the mixtures thereof present. In general, the dryingoil will be present in the compositions of the present invention inamounts ranging from about percent to about 50 percent by weight andmore preferably from about percent to about 35 percent by weight.

The carrier used in preparing the compositions of the present inventionshould be one in which the drying oil is substantially soluble and whichin the amounts used in the composition and in the actual confiningoperation will not be harmful to marine life. It will be recog nizedthat virtually any solvent or carrier if used in high enoughconcentrations may cause some damage to marine life at least in theimmediate vicinity of its usage. However, there are numerous liquidswhich can be used as carriers which have little or no effect upon marinelife in the concentrations employed. Non-limiting examples of suchcarriers include alcohols such as ethanol, propanol, butanol; esterssuch as ethyl acetate, amyl acetate and the like; ketones such asacetone, methyl isobutyl ketone, etc.; ethers such as diethyl ether,diisopropyl ether and the like, etc. Particularly preferred because ofavailability, and relative low cost are the liquid alcohols andespecially ethanol. Ethanol is easily obtainable, relatively non-toxicto marine life even in high concentrations, an excellent carrier formost of the natural as well as synthetic drying oils and readilymiscible with water. While the term carrier is employed, it is to beunderstood that in most cases the compositions of the present inventionwill be solutions such that the carrier will be a solvent as that termis commonly employed. However, due to the fact that in certaininstances, particularly in the case of drying oils derived from naturalsources, certain amounts of insoluble impurities may be present suchthat the compositions formed are not true solutions but rather containsome suspended matter, the term carrier is employed so as to encompasssuch situations.

In general, the carrier will be present in amounts ranging from about 50percent to about 90 percent by weight and more preferably from about 65percent to about 85 percent by weight.

ln employing the compositions of the present invention, it isadvantageous to employ a metallic soap catalyst which tends to speed upthe confining action of the composition on the oil spill. These metallicsoap catalysts are generally comprised of water insoluble soaps ofmaterials such as fatty acids as for example, stearic acid, oleic acidand the like; naphthenic acids; rosin; tall oils and other suchnaturally occurring products with heavier metals such as aluminum,calcium, cadmium, cobalt, copper, iron, lead, manganese, nickel, tin orzinc. Cobalt naphthenate has been found to be a particularly desirablemetallic soap catalyst. The insoluble metallic soap catalysts aregenerally obtained either by heating the respective fatty acid or thelike with a metallic oxide or carbonate or by the reaction of a solublesodium or potassium salt of the fatty acid, etc. with a solution of theparticular heavy metal salt. The metallic soap catalysts are to bedistinguished from the ordinary soaps which are the soluble salts of thefatty acids containing from about 12 to 22 carbon atoms and aregenerally the sodium, potassium or lithium salts of such fatty acids.

When a metallic soap catalyst is employed in the compositions of thepresent invention, it can be present in the composition as it is appliedto the oil slick or spill or in the alternate, a composition comprisedof the drying oil and the carrier can be applied to the oil slick afterwhich an amount of the metallic soap catalyst sufficient to fall withinthe above specified percentage can be applied to the oil slick.

Generally speaking, the metallic soap catalyst will be present in thecompositions of the present invention in amounts ranging from about ipercent to about 10 percent by weight and preferably from about 2percent to about 6 percent by weight.

As noted, the metallic soap catalyst is not absolutely necessary as thecompositions disclosed will confine the oil slick even in the absence ofsuch. However, it has been found that by the addition of one of themetallic soap catalyst the containment action of the compositions isspeeded up considerably in most cases.

it is to be understood that the term oil as used herein refers not onlyto crude oil but to various fractions thereof such as for example,gasoline, fuel oil, kerosene or any of the common petroleum cuts derivedfrom petroleum. When applying the compositions of the present inventionto the oil slick or spill, it will be apparent that the amount ofcomposition employed will be dependent upon the extent of the slick bothas to its thickness and the amount of area covered by the slick. As ageneral rule however, from about one half to about twice the amount byvolume of the oil spill, applied over the entire area of the spill, willsuffice to effect the desired confining of the oil. Greater amountshowever can be used, the only disadvantage being that the cost ofapplication rises without any appreciable increased effect on theconfining rate.

When employing the compositions of the present invention on an oil slickor spill, the composition, which of course is in liquid form, can besprayed on from hoses from a passing ship, can be dropped from aircraftat low levels or can be applied in any manner whereby the entire area ofthe oil slick can have dispersed upon it the compositions disclosedherein. in general, it is preferable to apply the composition in a finespray such as an aerosol to insure intimate contact with the oil slick.Within a short time, i.e., from one to five minutes,

after the composition has been dispersed upon the oil slick, a confiningbarrier of the composition will begin to form on the surface and aroundthe peripheral edges of the oil slick actually reducing the area of theslick. The time for forming the confining barrier will of course dependon the size of the slick and the amount of the confining compositionemployed. Once this confining action has taken place, the slick or spillmay be easily removed by mechanical means such as scooping. As notedabove, the advantages of using the compositions and methods of thepresent invention are most apparent where wave action would make the useof mechanical devices impossible. In fact, a certain amount of waveaction is desirable in that it tends to effect a more rapid formation ofthe confining barrier which in turn of course facilitates removal of theoil preferably by mechanical means.

In order to more fully demonstrate the invention, the

' following non-limiting examples are presented. Unless otherwiseindicated, all parts and percentages are by weight.

EXAMPLE 1 To a 500ml breaker approximately four inches in diameter andcontaining around 300 mls of tap water at about 72F was added 1 cc of30API crude oil. The oil quickly spread over the surface of the water inthe beaker forming a slick on the surface thereof which substantiallycovered the entire surface area of the water in the beaker. One cc of asolution containing 23 percent of a drying oil known as FLOAT R-22 marketed by Tenneco Chemicals, Inc., Pensacola, Florida, 74 percent ethanoland 3 percent cobalt naphthenate was atomized onto the oil floating onthe surface of the water in the breaker The FLOAT R-22 which is a talloil derivative had the following properties:

Acid Value 174.2 Rosin Acids 9.8% Fatty Acids (mainly oleic &

linoleic) 79.0% Esters and Unsaponifiables 11.6% Titre below 8C 16F Thebeaker was agitated for 2-3 minutes and it was noted that a containingfilm soon covered the oil slick and formed a barrier around the edges ofthe slick. It was further observed that the area of the slick wassubstantially reduced. Upon vigorous shaking, the oil slick, uponcessation of the agitation gathered in a relatively confined area andremained contained therein.

EXAMPLE 2 The procedure in Example 1 is followed with the exception thatthe drying oil is a material known as ACO- NEW 500 marketed by TennecoChemicals, Inc., Pensacola, Florida. ACONEW 500 comprises distilled talloil fatty acids and has the following properties: Acid Number 193Saponification Number 195 Iodine Numher 129 Rosin Acids 2.7% Fatty Acid94.8% Unsaponifiables 2.5% Titre 0C 4 Using the ACONEW 500, similarresults to those observed in Example I are obtained.

EXAMPLE 3 The procedure of Example 1 is repeated except a material knownas ACOFOR, marketed by Tenneco chemicals, Inc., Pensacola, Florida isemployed as the drying oil. ACOFOR comprises distilled tall oil fattyacids and has the following properties.

Acid Number 193 Saponificat jon Number 195 Iodine Number 129 Rosin Acids2.7% Fatty Acids 94.8% Unsaponifiables 2.5% Titre 0C 4 Results similarto those observed in Example 1 are obtained.

EXAMPLE 4 The procedure of Example 1 is repeated with the exception thata material known as ACOSIX marketed by Tenneco Chemicals, Inc.,Pensacda, Florida is employed as the drying oil. ACOSIX has thefollowing properties:

Acid Numer 190 Saponification Number 192 Iodine Number 140 Rosin Acids25% Fatty Acids 73% Unsaponifiables 2% Titre 0C 1 The results obtainedusing the ACOSIX are similar to those observed in Example 1.

Various modifications, changes, alterations and additions can be made inthe present method, and in the conditions and reagents for the method.All such modifications, changes, alterations and additions as are withinthe scope of the appended claims form a part of the present invention.

We claim:

1. A composition of matter useful in effecting confining of an oil slickon the surface of water consisting essentially of from about 10 to about50 percent by weight of a drying oil, said drying oil comprising amaterial containing a major proportion of a component selected from theclass consisting of unsaturated fatty acids, glycerides of unsaturatedfatty acids and mixtures thereof, from about 50 to about percent byweight ofa carrier selected from the class consisting of liquidalcohols, ketones and ethers, and from about one to about 10 percent byweight of a water insoluble metallic soap catalyst.

2. The composition of claim 1 wherein said carrier comprises a liquidalcohol.

3. The composition of claim 2 wherein said alcohol comprises ethanol.

4. The composition of claim 1 wherein said metallic soap catalystcomprises cobalt naphthenate.

2. The composition of claim 1 wherein said carrier comprises a liquidalcohol.
 3. The composition of claim 2 wherein said alcohol comprisesethanol.
 4. The composition of claim 1 wherein said metallic soapcatalyst comprises cobalt naphthenate.